Herbicide

ABSTRACT

A MIXTURE OF A PENOXYCARBOXYLIC ACID DERIVATIVE AND A BISCARBAMATE OR AN ACID ANILIDE WHICH HAS A GOOD HERBICIDAL ACTION AND A PROCESS FOR CONTROLLING UNWANTED PLANTS IN PREEMERGENCE TREATMENT WITH THIS MIXTURE.

States Patent Olhce 3,813,237. HERBICIDE Adolf Fischer, Mutterstadt, Germany, assignor to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafeu (Rhine), Germany a No Drawing. Filedv July 9, 1970, Ser. No. 53,661 Claims priority, application Germany, July 17, 1969, P 19 36 341.8 Int. Cl. Allln 9/24 US. Cl. 71-117 4 Claims ABSTRACT OF run DISCLOSURE A mixture of a phenoxycarboxylic acid derivative and a biscarbamate or an acid anilide whichhas a good herbicidal action and a process for controlling unwanted plants in preemergence treatment with this mixture.

The present invention relates to a mixture of phenoxy carboxylic acid derivatives and biscarbamates or acid anilides having a good herbicidal action. I

It is known to use substituted phenoxycarboxylic acids, diurethanes or acid anilides, a selective herbicidal agents; however, their action on weeds is not satisfactory.

" We have now found that herbicides comprising a mixture of I (a) a compound having the formula n mQ-m-drr-coom where X denotes chlorine or methyl, Y denotes chlorine or hydrogen, R denotes hydrogen or methyl and R denotes hydrogen or an alkyl radical (methyl, ethyl, isooctyl, isobutyl) or an alkoxy-alkyl radical (butyloxyethyl) or the salts of these compounds, and

(b)-a compound having the formula where R denotes hydrogen or haloalkyl (chloromethyl, bromoethyl, dichloropropyl, p-chloropropyl, 2,2-dimethyl- 2-chloroethyl, 1,1-dimethyl2-chloroethyl), or

(c) a compound having the formula where X denotes thiocyano, halogen (F, Cl, Br, I), the nitro group, a trifluoromethyl or alkyl radical having 1 to 3 carbon atoms (methyl, ethyl, propyl, isopropyl) or an alkoxy radical (methoxyl, ethoxyl, propoxyl), R denotes an aliphatic radical-having -l to 4 carbon atoms (methyl, yLr opy sop py b t s y t r W ly propenyl, methyl propenyl, chloromethyl, dichloromethyl, trichloromethyl, a,u-dichloroethyl, nz-ChlOIOethYl, p-chloroethyl, a,a-dichlorobutyl, a,a-dibromobutyl, wot-dimethylfl-bromoethyl, cyclopropyl) which may be substituted by chlorine, bromine, fluorine, cyano or thiocyano, R denotes an alkyl radical having 1 to 3 carbon atoms (methyl, ethyl, propyl, isopropyl) which may be substituted by halogen (F, Cl, Br, I) or R denotes an alkynyl radical having 2 to 5 carbon atoms (ethynyl, propynyl, butynyl, pentynyl), and n denotes one of the integers 0, 1, 2 and 3, have a good herbicidal action when employed preemergence.

3,813,237 Patented May 28, 1974 The special advantage of the mixtures according to the invention is that they have an excellent action when used preemergence on most monocotyledonous and dicotyledonous weeds.

By used preemergence we mean the application of the herbicides before the seedlings of the crop plants have thrust through the surface of the soil. The herbicides can therefore, either before or during sowing, be applied to the surface of the soil or evenly incorporated into the upper layer (down to about 5 cm.) of the soil. If the herbicides are applied after sowing, then at the latest shortly before the seedlings pierce the surface of the soil. Here, too, the herbicides may be applied to the surface of the soil or evenly incorporated into its upper layer.

The ratio of the individual components of the mixture to each other may vary within wide limits. 'It is, however, preferred to use a mixture of the individual active ingredients a:b or c in a weight ratio of from 3:1 to 1:5.

By salts we mean the alkali metal salts (potassium, sodium), the alkaline earth metal salts (calcium, magnesium) or the ammonium or amine salts (dimethylamine).

The herbicides according to the invention may be used as solutions, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a line distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, water, mineral oil fractions having a medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, cyclic hydrocarbons such as tetrahydronaphthalene, and alkylated naphthalenes are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents. Concentrates which are suitable for dilution with water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier.

The mixtures may be used alone or in admixture with insecticides, fungicides and fertilizers.

The following examples demonstrate the application of the herbicides according to the invention.

EXAMPLE 1 Loamy sandy soil is filled into pots and sown with the seeds of Zea mays, Sorghum vulgare, Setaria glauca, Dactylis glomerata, Poa annua, Lolium mwltiflorum, Echinochloa crus-galli, Chenopodium album and Raphanus raphanistrum. The soil prepared in this manner is then treated with the following individual active ingredients and mixtures thereof, each active ingredient and each mixture being dispersed or dissolved in 500 liters of water per hectare:

(I) dimethylamine salt of 2,4-dichlorophenoxyacetic acid,

1 and 4 kg. per hectare;

(II) dimethylamine salt of 2-(2-methyl-4-chlorophenoxy)- propione acid, 1 and 4 kg. per hectare;

(III) chloroacetic acid-N-butyn-(1)-yl-(3)-anilide, 3 and 4 kg. per hectare;

(IV) chloroacetic acid-N-3 methylbutyn-(1)-yl-(3)-anilide, 3 and 4 kg. per hectare;

(V) chloroacctic acid-N 3 methylbutyn-(1)-yl-(3)-mmethylanilide, 3 and 4 kg. per hectare;

Kg. per hectare It is ascertained after 3 to 4 weeks that, although the mixtures have the same good compatibility with crop The results of the experiment are given in the following table:

Active ingredient I II III I+III II+III KgJha 1.6 3. 1. 5 8 1. 6 3 l.6+1.6 1.54-1.15

Crop plants:

Zea may: O 10 O 10 0 l0 0 0 Sorghum vulgar: 0 0 55 0 l0 0 0 Unwanted plants:

Poa ammo 0 0 0 0 9B 100 100 100 0 0 0 0 8O 95 85 90 0 0 0 0 85 95 90 100 0 0 0 0 80 100 90 95 0 0 0 0 95 100 100 100 Chenopodium album 100 100 100 100 100 100 100 100 Amarathus rctroflezua 80 95 80 95 90 100 100 100 Norm-0 =No damage; 100 Complete destruction.

EXAMPLE 3 In a greenhouse, loamy sandy soil is filled into pots and sown with the seeds of Zea mays, Sorghum vulgare,

Active ingredient I II 111 IV v I+III I+IV 1+V 1I+III II+IV II+V KgJha 1 4 1 4 3 4 3 4 a 4 1+3 1+3 1+3 1+3 1+3 1+3 Crop plants:

Zea may; 0 20 0 20 0 0 0 0 0 0 0 0 0 0 0 0 Sorghum vulqare 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Unwanted plants:

Setaria glauca 0 0 0 0 95 100 95 100 90 100 95 95 90 100 100 95 Doug/It's alomemta- 0 0 0 90 100 95 100 85 95 90 95 e5 95 95 90 Poo ammo 0 5 15 95 100 100 100 100 100 95 100 100 100 100 100 Loliurn multifiorum. 0 5 10 so 100 95 100 100 100 95 95 100 95 100 100 Echirzochloa m m 0 0 0 90 100 100 100 100 100 100 100 100 100 100 100 Chenopo diam album 100 100 40 50 0 a0 30 30 100 100 100 100 100 100 Raphan'ua rapbanistrum. 100 100 5 20 0 10 5 10 100 100 100 100 100 100 NOTE.0= No damage; 100=Complete destruction.

EXAMPLE 2 Echinochloa crus-galli, Digitaria sanguinalis, Lolium erenne Stellaria media and Sinapis arvensis The soil is sand soil 1s filled into ots and sown with the p Loamy y p 40 then treated with the following active ingredients and seeds of Zea mays, Sorghum vulgare, Poa annua, Alopecurus myosuroides, Digitaria sanguinalis, Echinochloa crus-galli, Setaria viridis, Galium aparine, Chenopodium album and Amaranthus retroflexus. The soil prepared in this manner is then immediately treated with the following active ingredients and mixtures thereof, each active ingredient and each mixture being dispersed or dissolved in 500 liters of water per hectare:

Kg. per hectare I+III 1.5+1.5 II+III 1.5+1.5

It is ascertained after 3 weeks that, although the mixtures have the same good compatibility with crop plants as the individual active ingredients, the mixtures do have a superior herbicidal action.

mixtures thereof, each active ingredient and each mixture being dispersed in 500 liters of water per hectare:

Kg. per hectare I+II 1+3 I+III 1+3 I+IV 1+3 After 4 weeks, the mixtures show, compared with the individual active ingredients, a superior compatibility with the crop plants and exhibit an excellent herbicidal action.

The results of the experiment are given in the following table:

Active ingredient I II III IV I+III I+III I+IV kgJha 1 4 a 4 a 4 a 4 1+3 1+3 1+3 Crop plants:

Zea may: 0 25 0 20 O 0 0 0 0 0 0 Sorghum vulaare 0 30 0 30 0 0 0 0 0 0 0 Unwanted plants:

Edtinocbloa mnaalli- 0 20 90 100 100 100 100 100 90 100 100 Diqitan'a aanauinalia. 0 25 95 100 95 100 100 100 95 95 100 Lolium pererme.-.. 0 5 85 100 95 100 80 85 Stellaria media- 80 5 10 0 5 5 15 90 85 90 Sinapin arverm'a 90 100 10 30 0 15 10 20 100 90 100 NOTE .0= N0 damage; 100= Complete destruction.

5 EXAMPLE '4" the following active ingredients and mixtures thereof, each active ingredient and each mixture being dispersed in 500 liters of water per hectare:

(I) a-(2,4-dichlorophenoxy)-propionic acid, 1.5 and 3 kg.

that of I+II and I+III:

Z-methyl-4-chlorophenoxyacetic acid+N-(1-chioromethylpropyD-carbamic acid-(m-carbomethoxyaminophenyl)-ester.

EXAMPLE 5 Loamy sandy soil is filled into pots and sown with the seeds of Zea mays, Sorghum vulgare, Setaria glauca, Dactylis glomerata, Poa annua, Lolium multiflorum, Echinochloa crus-galli, Chenopodium album and Raphanus rephamistrum. The soil prepared in this manner is P hectare, then treated with the following active ingredlents and P Y P PY mixtures thereof, each active ingredient and each mixture methoxyamrnophenyD-ester, 1.5 and 3 kg. per hectare; being dispersed in 500 liters of water per hectare:

(HI) N-(1,1-d1methyl-2-chloroethyl)-carbam1c acid-(mcarbomethoxyaminophenyl)-ester, 1.5 and 3 kg. per 2l4'dlchlol'oph6119134166"c 8614, 0- 1, 3 and 6 P hectare; ll 2 th 14 h h -me -c o o Kg per hectare 5)and(6 k gr hem: r p enoxy) propionic acid, 1, 2,

1 +111 1 s 1 5 (III) chloroacetic acid-N-butyn-(1)-yl-(3)-amhde, 2.5, 3

and 5 kg. per hectare; After 3 to 4 weeks, the mixtures, compared with the (IV) chloroacetic acid N 3 methylbutyn-(l)-yl-(3)- individual active ingredients, exhibit a good herbicidal anilide, 5 and6kg. per hectare;

action and have good crop plant compatibility. (V) chloroacetic acid N 3 methylbutyn-(1)-yl-(3)- The results of the experiment are given in the following m-methylanilide, 5 and 6 kg. per hectare;

table:

Kg. per hectare Active ingredient fig I II III I+II r+1rr 1+v +5 KgL/ha 1.5 a 1.5 s 1.5 3 1.o+1.5 1.5+1.o II+IH Crop plants H+Iv 1 +5 Zea ma 0 1o 0 1o 0 o 0 o 1+5 l Sorghum volume 0 20 0 10 0 10 0 0 g g gfig z After 3 to 4 weeks, it IS ascertained that the mixtures galli o 0 so 100 so go so so have the same good compatibility as the individual active 1) r i 21 1x 2 0, o 85 95 80 90 85 80 ingredients with the crop plants, but a superior herbicidal Stelturiamedim... so 100 so 65 so 100 I00 actlon- 901mm W The results of the experiment are given in the following NorE.-0=No damage; 100=Comp1ete destruction. table:

Active ingredient 1 II III 1V V I+III I+IV I+V II+III II+IV II+V KgJha 0.6 1 a 0 1 2 o o 2.5 a o o o o o o.o+2.o 1+5 1+5 2+3 1+o 1+5 Crop plants:

Zea muv o 0 10 so 0 o 30 so 0 o o o 10 0 1o 0 o 0 o o o Sorghum vulaare 0 0 20 40 0 0 30 60 0 0 0 0 50 0 10 0 0 0 0 0 0 Unwanted plants:

Stellaria qlauca o o 0 20 o o 1o 20 s so 100 100 500 too too so 100 100 so 100 100 Ductulisalomerata-. 0 o o 10 0 0 1o 20 so so 100 too 100 100 100 so 100 100 100 100 PM ammo o o 0' 2o 0 o 20 so 90 100 100 100 100 on too 100 mo 100 100 Lo1iu1n1nultifiorum o o o 10 o o 20 so so so so 100 ooo 100 100 so 100 100 so 100 100 Echinochloacrua-aallL- o o 0 2o 0 o 0 20 so so 100 100 too 100 100 so too 100 so 100 100 Chexopodium album... so 100 100 100 too too too 100 so 40 so 40 40 40 so 100 100 100 100 100 100 figli'iii'iatmm so too 100 100 too too 100 100 o o 15 2o 40 2o 40 so 100 100 100 too 100 No'rn.-0=No damage; 1 0o=- Complete destruction.

The action of the followingmixtures corresponds to EXAMPLE 6 (I) dimethylamine salt of 2,4 dichlorophenoxyacetic acid, 1, 2 and 3 kg. per hectare;

(H) sodium salt of 2-methyl-4-chlorophenoxyacetic acid,

1, 2, and 3 kg. per hectare;

(III) N (1 chloromethylpropyl) carbamic acid-(3'- carbomethoxyaminophenyl)-ester, 1, 2 and 3 kg. per hectare;

Kg. per-hectare I+III 1+2, 2+1 II+III 1+2, 2+1

After 3 weeks, it is ascertained that the mixtures, compared with the individual active ingredients, have a superior herbicidal action and good compatibility with the crop plants.

The results of the experiment are given in the following:

media and Galium aparine. The soil is then treated with the following active ingredients and mixtures thereof, each active ingredient and each mixture being dispersed in 500 liters of water per hectare:

Active ingredient I II III I+III II+III Kg /he---::-::::;::.:.:.:.: 1 2 3 l 2 8 1 2 3 1+2 2+1 1+2 2+1 Crop plant:

Zeamnv: e 0 10 0 0 l0 0 0 l0 0 0 0 0 Sorghum vulpare... 0 10 20 0 10 0 0 10 0 l0 0 10 Triticum vulqare- 0 0 15 0 0 15 0 0 l6 0 0 0 0 Unwanted plants:

Poe annuu 0 0 0 0 0 0 90 95 100 95 90 95 90 Alopecurmmyoauroidn- 0 0 0 U 0 0 80 90 95 90 80 90 80 Diaitaria mnauinflic"-.. 0 0 0 0 0 0 80 9O 95 90 80 90 80 Echinochloa crua-qaili. 0 0 0 0 0 0 80 90 100 90 80 90 80 Setaria viridi| 0 0 0 0 0 0 90 95 100 95 90 95 90 Galeopaia up 80 100 100 80 100 100 30 60 70 100 100 100 100 Amaranth! retroflezus 76 90 95 76 90 95 90 95 100 100 100 100 100 NOTE.0=N0 damage; 100=Cornpleto destruction.

EXAMPLE 7 In a greenhouse, loamy sandy soil is filled into pots and sown with the seeds of Zea mays, Sorghum vulgare, Echinochloa crus-galli, Digitaria sanguinalis, Lolium perenne, Stellaria media and Sinapis arvensis. The soil is then treated with the following active ingredients and mixtures thereof, each active ingredient and each mixture being dispersed in 500 liters of water per hectare:

(I) 2-(2,4-dichlorophenoxy)-propionic acid, 0.5, l, 2 and 3 kg. per hectare; (II) 2- (4-chloro-2-methylphenoxy)-propionic acid, 0.5, 1,

2 and 3 kg. per hectare; (III) N-(l-chloromethylpropyl) carbamic acid-(3-carbomethoxyaminophenyl)-ester, l, 1.5, 2 and 3 kg. per

hectare;

Kg. per hectare I+III 2+1, 1+2, 0.5+1.5

II+III 2+1,1+2,0.5,+2.5

After 3 to 4 weeks, it is ascertained that the mixtures have the same good compatibility with crop plants as the individual active ingredients, but a superior herbicidal action.

t;lhe results of the experiment are given in the following ta 1e:

Active ingredient I II III I+III II+III Kg.Iha-..' 0.5 1 2 3 0.5 1 2 3 1 1 5 2 3 2 1 0 5 2 1 0.5 Crop plants:

Zea. may; 0 0 0 10 U 0 0 10 U 0 0 10 0 0 0 0 0 0 Sorghum vulpare 0 0 10 20 0 0 0 15 0 0 0 10 10 0 0 0 0 0 Unwanted plants:

Echinochlo Cr'uwfllli. 0 0 0 10 0 0 0 o 80 a5 90 100 so 90 B5 80 90 a5 Digitaria aagunalia" o 0 0 10 0 0 0 0 so 35 90 95 s0 90 as so e0 e5 Stellaria media"--. 70 80 90 100 70 so 95 100 60 10 so 90 100 100 100 100 100 100 Galium aparine 60 70 80 90 60 70 80 90 20 30 40 70 100 100 100 100 100 95 NOTE.O=N0 damage; 100=Comp1ete destruction.

Kg. per hectare EXAMPLE 9 I+II 0.5+2.5 I+III 1+5 In a greenhouse, loamy sandy soil is filled into pots and I+IV 1+5 sown with the seeds of Zea mays, Echinochloa crus- After 4 weeks, it is ascertained that the mixtures have 4 Galmm apanfze and Mamfana f f a herbicidal action superior to that of the individual active 5 The $011 treated with the fqlloivmg afmve ingredients. gredrents and mixtures thereof, each active ingredient and The results of the experiment are given in the following each mixml'fis being dispersed in 500 liters of Water P table: hectare:

Active ingredient I II III IV I+II I+III I+IV Kg.lha.::.:-.:.:;:.:.:.:.:;;:.:.:.:.:.;. 0.5 1 3 6 2.6 3 5 6 6 6 (NH-2.6 1+5 1+6 7 Crop plants:

Zea maul. I..'.:.:.;: O 0 1O 40 0 0 O 10 0 I0 0 0 U Sorghum vulgar: 0 0 20 0 0 0 10 0 10 0 0 0 Unwanted plants:

Echinochloa crud-quilt 0 o 10 40 35 90 100 100 100 100 as 100 100 Diaitaria aanguinalin- 0 0 10 40 90 95 100 100 100 100 90 100 100 Lolium perenne o 0 0 20 so 35 100 100 100 100 80 100 .100 Stellaria media... so 100 100 0 ii 20 a0 40 70 100 100 Sinapil aruemia so 100 is 10 e0 40 a0 40 90 100 100 Norm-0 =No damage; 100=Compiete destruction.

EXAMPLE 8 (I) potassium salt of 2,4,S-trichlorophenoxyacetic acid, 1, In a greenhouse, loamy sandy soil is filled into pots and I 3 P 4 Per hectarfii sown with the seeds of Zea mays, Sorghum vulgare, lsooctyl P Y)'p p i Echinochloa crus-galli, Digitaria sanguinalis, Stellaria 75 2 and 3 kg. per hectare;

9 (III) N-(l-chloromethylpropyl) carbamic acid-(3-carbomethoxyaminophenyl)-ester, 1.5, 2 and 3 kg. per hectare; (IV) chloroacetic acid-N-butyn-1-yl-3-anilide, 2.5, 3 and 4 kg. per hectare;

10 of the plants is to be prevented are treated with a mixture consisting essentially of (a) 2,4-dichlorophenoxyacetic acid or a salt thereof,

and (b) a compound having the formula 5 Kg. per hectare I+III 1+2 1+1v II+III 0.5 to 1.5 wherein X is methyl, n is or 1, R is chloroalkyl hav- II+IV 0.5+2.5 10 ing 1-3 carbon atoms and R is butynyl or methylbutynyl in a weight ratio of a to b in the range of 3 :1 After 4 to 5 weeks, the following results are obtained: to 1:5.

Active ingredient;

I II III Iv I+III I+IV II+III II+Iv KgJha 1 3 4 0.6 2 a 1.5 2 a 2.5 a 4 1+2 1+3 0. 5+1.0 0. 5+2.& Crop plant: Zea may|. 0 20 30 0 20 30 0 0 0 0 0 0 0 0 O Unwanted plants:

Echtnochloa mus-gall! r 0 10 0 10 90 100 100 90 80 80 P06 annua 0 10 20 0 10 a0 95 95 90 95 100 100 95 95 9o Galium aparine 30 50 70 70 100 100 30 40 70 10 16 25 80 50 100 89 Matrtearia chmomilla--- "1.--- 80 100 100 75 100 100 so so 100 40 so so 100 100 100 100 NOTE.--0=NO damage; 100=Complete destruction.

We claim: 4. A process as claimed in claim 3 wherein compound a 1. A herbicide for preemergence application consistlng 25 1s 2,4-dich1orophenoxyacetic acid and compound b is chloessentially of a mixture of (a) 2,4-dichlorophenoxyacetic acid or a salt thereof,

and (b) a compound having the formula roacetic acid-N-butyn-( 1 )-yl-(3 -anilide.

References Cited UNITED STATES PATENTS 3,133,808 5/1964 Hamm 71-117 X 3,345,151 10/1967 01in 71-117 X 3,535,377 10/1970 Steinbrunn et a1. 71-118 X FOREIGN PATENTS 4,012,197 6/1965 Japan 71-118 JAMES O. THOMAS, 1a., Primary Examiner US. Cl. X.R. 

